Textile printing composition



Patented May 1, 1945 TEXTILE PRINTING COMPOSITION v Roy A. Pizzarello,Mount Vernon, N. Y., asslgnor to Interchemical Corporation, New York, N.Y., a corporation of Ohio.

No Drawing. Application May 22, 1941, Serial No. 394,624

1 Claim.

nated with a compound capable of coupling with a diazo compound, and theprinting paste is made up withthe diazo compound. In another method, theprinting paste contains both the coupling compound and the diazocompound, which is stabilized against coupling by'the conversion of thediazo compound into a compound which is stable in alkali, but whichreforms the active diazo compound on exposure to acid.

Coupling with substituted amines containing water-solubilizing groups isa preferred method of forming such coupling stabilized compounds; theresultant water-soluble triazenes (diazoamino and diazoimino compounds)are compounded with alkali acid coupling components,-

and' made up into printing pastes'in conventional fashion.

Such water-soluble triazenes are of rather recent origin, having beenevolved within the last twenty years to meet the need of the trade for ameans of printing ingrain azo colors without the necessity forpre-impregnating'the fabric. The older corresponding water-insolubletriazenes, made from amines not containing watersolubilizing groups,were never used because they could not be 'iispersedin water to makesatisfactory printing pastes with the conventional water-dispersiblethickeners.

In the copending application ,of Albert E. Gessler and myself-Serial No;337,490, filed May 27, 1940, which issued on Feb. 2, 1943, as Patent No.2,309,946there is described a type of printing paste which, for thefirst time, successfully employs water-insoluble triazenes.

These composition comprise essentially water-- insoluble tria'zenes ofthe group consisting of diazoamino and diazoimino compounds which canbereconverted into diazo compounds by aqueous acid uniformly dispersedthrough a hydrophobic liquid capable of forming stable water-in-organicliquid emulsions, most preferably water immiscible lacquers. Prior toprinting, these composition are converted to waterin-organic liquidemulsions.

In the preferred form of that invention, the emulsion is formed with anaqueous solution of a compound capable of coupling with the diazocompound formed from the triazene, so that the final printing pastecontains one dyestufl component in solution in-the water phase of theemulsion, and the other uniformly dispersed through the organic phase.On printing, the coupling component in aqueous solution is absorbedinto, the cellulose fibers forming the yarns of the fabric, and thetriazene is deposited on the outside of the fibers and yarns. Whenexposed to steam and acid fumes in an acid ager, the triazene isconverted to the soluble diazo salt, which then couples with thecoupling component. Since the coupling component is already fixed in thefibers in sharp outlines, the color is formed in these sharp outlines,and the resultant print is extremely sharp.

In another form of that invention, the emulsion is treated beforeprinting with an aqueous acid solution added directly or preferably inthe form of another emulsion. This aqueous acid solution converts thetriazene to the water-soluble diazo salt which transfers from theorganic into the aqueous phase; the resultant printing paste is astandard dyestufi solution-in-organic liquid emulsion paste, and may beprinted on grounds prepared by impregnation with the coupling component.The principal advantage in this type of paste is that thewater-insoluble triazenes are perfectly stable over extended periods inall hydrophobe organic solvents whether they are soluble or insoluble inthem. Furthermore, these compounds, after conversion to thewater-soluble diazo state, in the emulsion, are stable for several timesas long as the same compound in conventional printing pastes.

The degree of dispersion of the triazene in the organic medium has apronounced effect on the color of the prints. The dispersed compoundshould be at least microscopically dispersed-4. e. as particleswhich-are not individually visible to the naked eye, and should mostpreferably be in solution in the solvent to obtain optimum color value.

azine bis-diazoimino compounds; and that these compounds may also beemployed in conventional water-pastes provided they are distributedmicroscopically, or smaller. This effect may be obtained by dissolvingthem in a water-miscible solvent, and adding the solution to the paste.

While water-soluble triazenes made from piperazine acetic acid have beenused in printing pastes (see British Patent No. 423,587), these productsare distinctly less advantageous than mine, since only, one molarequivalent of diazo compound is stabilized per mol of their piper'a- Yzine derivative. With piperazine itself the molar combining ratio is twoto one.

Typical examples of my invention are as follows:

A. PREPARATION OF PIPERAZINE DIAZO- NIUM COMPLEXES EXAMPLE A1Stabilization of -nltro-2-amino anisol .azine hexahydrate and 25 gramsof sodium carbonate at 0 C. A yellow fiocculent precipitate wasimmediately formed. This mixture was stirred until there was no morefree diazo present. The precipitate was then filtered, washed and dried.The yellow powder obtained weighed 24.2 grams (76.2%).

EXAMPLE A2 Stabilization of 4-chlor0-2-amino anisol One tenth mol (19.4grams) of 4-chloro-2- amino anisol hydrochloride was pasted with 50 cc.of hot water. To this paste 250 cc. of cold water and ice was added.When the temperature reached 10 C., 15 cc. of MN hydrochloric acid wereadded. Diazotization was brou ht about by the addition of 7.0 grams ofsodium nitrite in 2500. of water. After keeping the mixture at 10l2 C.for one-half hour, the solution was clarified andfiltered. The clearyellow colored filtrate was slowly added to a solution of 9.7 grams (.05M) of piperazine hexahydrate and 25 grams sodium carbonate. held at 0 C.until coupling'was complete. The

.colored precipitate was filtered, washed and dried.

The tan powder weighed 20.4 grams (70%),

' EXAMPLE A3 Stabilizati n of dianisidine One tenth mol (24.4 grams) ofdianisidine was dissolved in 20 cc. of 1ON hydrochloric acid. To effectdissolution heat was required. When solution was completed the mixturewas cooled to 0-5 C. by the addition of ice and water. To the coldsolution 30 co. more of 10N hydrochloric acid were added, followed bythe addition of 14.0 grams of sodium nitrite in 50 cc. of water.Tetrazotization was continued for 30 minutes, when the solution wasclarified and filtered. The light brown tetrazo solution was thencoupled at 0 C. in the presence of sodium carbonate with 19.4 grams (onetenth mol) of piperazine hexahydrate. The precipitate was filtered,washed and dried. 29.1 grams (84.1%) of a tan powder was obtained.

EXAMPLE A4 Stabilization of ortho chlor aniline One tenth mol (12.7grams) of O-chlor aniline are suspended in 250 cc. of water and 25 cc.of 10N hydrochloric acid added. The mixture is cooled to 10 C. by theaddition of ice. A- solution of 7.0 grams sodium nitrite in 25 cc. ofwater The temperature was to a solution of 9.7 grams (.05 mol) ofpiperazine hexahydrate and 25 grams of sodium carbonate in water.Coupling takes place at 0 C. The resulting precipitate is filtered,washed and dried.

.The light cream colored powder weighed 27.5

grams (76%).

EXAMPLE A5 Stabilization of4-nit1'O-2-amino anisol 16.8 grams (0.1 mol)of 4-nitro-2-amino anisol are suspended in 250 cc. of water and25 cc. of10N hydrochloric acid added. Ice is added to cool to 10-15 C. 7.0 gramsof sodium nitrite dissolved in 50 cc. of water is added rapidly and themix allowed to stir for 45 minutes, when it is clarified and filtered.The clear yellow colored diazo solution is slowly added at 0 C. to asolution of 9.7 grams of piperazine hexahydrate and 25 grams of sodiumcarbonate. A yellow precipitate formed immediately. This material wasisolated, and the resulting yellow powder weighed 23.8 grams (75% yield)EXAMPLE A6 Stabilization of 4-chloro-2-amino toluene One tenth mol (14.2grams) of 4-chloro-2- amino toluene were added to cc. of hot water. Then25 cc. of 10N hydrochloric acid were added and the solution diluted withice and water to .500 cc. so that the temperature was lowered to 10-12C. During the course of 5 minutes, 7.0 grams of soduim nitrite in 25 cc.of water were added. Diazotization was continued for ari additional 25minutes, when the solution was clarilied and filtered. The clear yellowfiltrate was added to a water solution of 9.7 grams (.05 mol) ofpiperazine hexahydrate and 25 grams of sodium carbonate at 0 C. Thetemperature was maintained at 0 C. until coupling was complete. Thefaintly yellow precipitate was filtered, washed and dried. The resultingfaintly yellow powder weighed 26.5 grams (68.0%).

Other known diazotized amines which can be 7 stabilized by-the sametechnique include the diazo derivatives of the following:

6-benzoyl amino-4-amino-meta-xylene 2 nitro-para-anisidlneAlpha-naphthylamine Beta-naphthylamine Benzidine 3:3 dichlor-benzidineTolidine 4-amino-diphenyl-amine 4-amino-4' methoxy-diphenyl amine4-amino-3 methoxy-diphenyl amine l-amino-anthraquinone EXAMPLE B1 Aquantity of complex containing 1 gram of active diazo compound wasdissolved in water to make 40 cc. This was emulsified into a.waterin-lacquer emulsion comprising- 150 grams Solvesso #2 (hydrogenatedpetroleum naphtha-B. R. 135 to 177 C.)

X parts by weight coupling component (see table) in the aqueousphase I Xparts by weight 40% NaOI-I (see table) in the aqueous phase.

5 made to 100 parts by weight, with water.-

- 51.8 grams toluene P1 1 2 5? N hth 1 t Wit 80%!!! erazine com ex or aano com on or p p ink p m ink hydroxide 5-nitro-2amino anisole 2. 44Naphthol AS (anilide of beta-oxyuaphthoic 1. 56 2.

ac: 4-chlor-2-amino anisole 2. 40 Naphthol AS-OL (ortho-anisidide oibeta-oxy 1. 60 2.0

I naphthoic acid).

1. 63 Naphthol AS 2. 37 2. 2.35 1.65 2.0 2. 44 do l. 56 2. 0 4chlor-2-aminotoluene 2 30 Naphthol AS-D (ortho-toluidid oi beta-oxy l.70 2. 0

naphthoic acid).

5.0 grams concentrated emulsion consisting of 31.0 parts by weight alkydresin (glycerol phthalate modified with 35% soya oil) 27.0 parts byweight of a solution of milled rubberv in Solvesso #2.

3.0 parts by weight linseed oil 8.0 parts by weight Solvesso #2 25.0parts by weight aqueous NaCl solution 4.0 parts by weight sulfonatedtannin 2.0 parts byweight 80% aqueous acetic acid Suflicient sulfuricacid to hydrolize the triazene (1.3 grams for monoamines, 2.5 fordiamines) was then emulsified into the lacquer, as 20 cc. of an aqueoussolution. Hydrolysis took about 15 above paste, gave satisfactory printsof good color value.

EXAMPLE B2 Emulsion pastes for printing on 'unpz'gment'ed cloth Printingemulsions were also made from each of these complexes according to thefollowing formulation:

2.8 grams butanol 41.4 grams water parts by weight Solvesso #2 X partsby weight trlazene (see table) in the ganic phase EXAMPLE B3 Waterpastes The equivalent amounts (see above) of the pigment components foreach of the colors were mixed into the following paste:

minutes. A 20% sodium acetate solution made 25% sodium hydroxide 4.5 pto 20 W then added to buffer the acid; 35 'Cellosolve (ethylene glycolmonoethyl ether) 10.0 the resultant paste was grams of a watertr lstaroh-tragacanth thickening 70.0 in-lacquer emulsion containing theactive diazo Pigment components 4.0 compound in the interior phase,ready to print w t 11.5

on cloth impregnated with coupling components.

Each of Examples A1 to A6 made up into the 40 The triazene is dissolvedin the cellosolve before Obviously, the examples may be multipliedindefinitely without departing from the scope of my invention, which isdefined in the claim.

I claim:

A textile printing paste comprising an emulsion, the inner phase ofwhich is an aqueous alkaline solution of a diazo coupling component, andthe outer phase of which is a microscopic dispersion of apiperazIne-bis-diazoimino com- 7 pound in which both heterocyclicnitrogens of the piperazineare attached to a diazo group in ahydrophobic liquid capable of forming stable water-in-organic liquidemulsions.

- nova. mam-Lo.

